Fluorescent ovalbumin-functionalized gold nanocluster as a highly sensitive and selective sensor for relay detection of salicylaldehyde, Hg(II) and folic acid.

A sensitive and selective relay-based scheme for the detection of salicylaldehyde, Hg2+, and folic acid (FA) has been demonstrated using fluorescent ovalbumin functionalized gold nanoclusters (OVA-AuNCs, λem = 655 nm) in this article. The OVA-AuNCs were conjugated to salicylaldehyde via an imine linkage to form Salic_OVA-AuNCs conjugate. The molecular docking study reveals that multiple functional groups and amino acid residues are involved in the interaction between salicylaldehyde and the OVA-AuNCs. The coupling of salicylaldehyde with OVA-AuNCs results in fluorescence quenching at 655 nm and concomitant formation of an emission band at 500 nm, which have leveraged to detect salicylaldehyde down to 2.02 µM. Following that, the Salic_OVA-AuNCs has been used for the detection of Hg2+ and FA. Several processes, such as internal charge transfer (ICT), photoinduced electron transfer (PET) and metallophilic interactions, are involved between the Salic_OVA-AuNCs nanoprobe and the analytes, which allowed to detect Hg2+ and FA down to 0.13 nM and 0.11 nM, respectively. The Salic_OVA-AuNCs nanoprobe has an additional naked-eye utility when applied to paper-strip sensing strategy for Hg2+ and FA detection.

Precipitous change of the irreversible strain limit with heat-treatment temperature in Nb3Sn wires made by the restacked-rod process.

The intrinsic irreversible strain limit εirr,0 of Nb3Sn superconducting wires, made by the restacked-rod process and doped with either Ti or Ta, undergoes a precipitous change as a function of temperature θ of the final heat-treatment for forming the A15 phase. Nb3Sn transitions from a highly brittle state where it cracks as soon as it is subjected to an axial tensile strain of any measurable amount, to a state more resilient to tensile strain as high as 0.4%. The remarkable abruptness of this transition (as most of it occurs over a range of only 10 °C) could pose real challenges for the heat-treatment of large magnets, such as those fabricated for the high-luminosity upgrade of the Large Hadron Collider (LHC). We named this behavior the strain irreversibility cliff (SIC) to caution magnet developers. The approach to fulfilling application requirements just in terms of the conductor's residual resistivity ratio RRR and critical-current density Jc is incomplete. Along with RRR and Jc wire specifications, and sub-element size requirements that reduce wire magnetization and instabilities effects, SIC imposes additional constraints on the choice of heat-treatment conditions to ensure mechanical integrity of the conductor.

Barrierless Proton Transfer in the Weak C-H···O Hydrogen Bonded Methacrolein Dimer upon Nonresonant Multiphoton Ionization in the Gas Phase.

Intermolecular proton transfer (IMPT) in a C-H···O hydrogen bonded dimer of an α,ß-unsaturated aldehyde, methacrolein (MC), upon nonresonant multiphoton ionization by 532 nm laser pulses (10 ns), has been investigated using time-of-flight (TOF) mass spectrometry under supersonic cooling condition. The mass peaks corresponding to both the protonated molecular ion [(MC)H+] and intact dimer cation [(MC)2]•+ show up in the mass spectra, and the peak intensity of the former increases proportionately with the latter with betterment of the jet cooling conditions. The observations indicate that [(MC)2]•+ is the likely precursor of (MC)H+ and, on the basis of electronic structure calculations, IMPT in the dimer cation has been shown to be the key reaction for formation of the latter. Laser power dependences of ion yields indicate that at this wavelength the dimer is photoionized by means of 4-photon absorption process, and the total 4-photon energy is nearly the same as the predicted vertical ionization energy of the dimer. Electronic structure calculations reveal that the optimized structures of [(MC)2]•+ correspond to a proton transferred configuration wherein the aldehydic hydrogen is completely shifted to the carbonyl oxygen of the neighboring moiety. Potential energy scans along the C-H···O coordinate also show that the IMPT in [(MC)2]•+ is a barrierless process.

Evidence from EXAFS for Different Ta/Ti Site Occupancy in High Critical Current Density Nb3Sn Superconductor Wires.

To meet critical current density, J c , targets for the Future Circular Collider (FCC), the planned replacement for the Large Hadron Collider (LHC), the high field performance of Nb3Sn must be improved, but champion J c values have remained static for the last 10 years. Making the A15 phase stoichiometric and enhancing the upper critical field H c2 by Ti or Ta dopants are the standard strategies for enhancing high field performance but detailed recent studies show that even the best modern wires have broad composition ranges. To assess whether further improvement might be possible, we employed Extended X-ray Absorption Fine Structure (EXAFS) to determine the lattice site location of dopants in modern high-performance Nb3Sn strands with J c values amongst the best so far achieved. Although Ti and Ta primarily occupy the Nb sites in the A15 structure, we also find significant Ta occupancy on the Sn site. These findings indicate that the best performing Ti-doped stand is strongly sub-stoichiometric in Sn and that antisite disorder likely explains its high average H c2 behavior. These new results suggest an important role for dopant and antisite disorder in minimizing superconducting property distributions and maximizing high field J c properties.

Hydrogen bond induced HF elimination from photoionized fluorophenol dimers in the gas phase.

In this paper, we report finding of a remarkable chemical effect of hydrogen bonding, elimination of hydrogen fluoride (HF) from the hydrogen bonded dimers of 2-fluorophenol (2-FP) and 3-fluorophenol (3-FP), in a supersonic jet expansion upon multi-photon ionization using 4th harmonic wavelength (266 nm) of a Q-switched Nd:YAG laser, and the reaction has been probed by time-of-flight mass spectrometry. No HF elimination is observed to occur by such means from the monomer of 3-FP, but it occurs with a small yield from the monomer of 2-FP. On the other hand, upon dimerization the reaction is triggered on for 3-FP, and for 2-FP it becomes so facile that no intact dimer cation survives and only the HF eliminated product ion appears in the mass spectra. Electronic structure calculation shows that in the cationic ground (D0) state, although the reaction for 2-FP dimer is exothermic, the associated barrier is significantly high (2.75 eV) and for its occurrence, absorption of three photons (2+1 type) is required. However, the reaction is predicted barrierless in the intermediate S1 state of this dimer, and HF loss dimer cation mass peak could appear in the mass spectrum due to an effective two-photon (1+1) ionization process. In the case of 3-FP dimer, the energy barriers both in S1 (neutral) and D0 (ionic) states are high, and it is suggested that for occurrence of HF elimination, dimer cation needs to absorb an additional photon. For facilitation of HF loss from this dimer cation, a rearrangement of the geometry and formation of an intermediate adduct have been suggested, and it is argued that the latter could be produced by nucleophilic attack of the neutral moiety at the ortho site of the cationic counterpart.

Keto-enol tautomerization and intermolecular proton transfer in photoionized cyclopentanone dimer in the gas phase.

Time-of-flight mass spectra of cyclopentanone and its clusters cooled in a supersonic jet expansion have been measured following 4-, 3-, and 2-photon ionizations by the 2nd, 3rd, and 4th harmonic wavelengths, respectively, of a Q-switched Nd:YAG laser. The mass spectra reveal signatures of energetically favored keto to enol tautomerization of the molecular ion leading to intermolecular proton transfer, and this observation is found sharply dependent on the ionization wavelengths used. Electronic structure calculation predicts that in spite of the energetic preference, keto-enol conversion barrier of isolated molecular ion is high. However, the barrier is significantly reduced in a CH⋯O hydrogen-bonded dimer of the molecule. The transition states associated with tautomeric conversion of both cyclopentanone monomer and dimer cations have been identified by means of intrinsic reaction co-ordinate calculation. In a supersonic jet expansion, although a weakly bound dimer is readily generated, the corresponding cation and also the protonated counterpart are observed only for ionization by 532 nm. For other two ionization wavelengths, these species do not register in the mass spectra, where the competing reaction channels via α-cleavage of the ring become dominant. In contrast to the report of a recent study, we notice that the intact molecular ion largely survives fragmentations when ionized from the 2-photon resonant 3p Rydberg state as intermediate using nanosecond laser pulses, and the corresponding resonant 3-photon ionization spectrum has been recorded probing the intact molecular ion.

Signatures of isomerization in photodissociation of trans- crotonaldehyde probed by multiphoton ionization mass spectrometry.

We report the observation of new isomerization effects in the UV-photodissociation of trans-crotonaldehyde upon multiphoton excitation by the third harmonic (355 nm) pulses of a Nd:YAG laser. A time-of-flight mass spectrometric analysis reveals formation of acetaldehyde, acetyl, and methoxy radical cations as signatures of isomerization processes. A small segment of the multiphoton ionization spectrum of jet-cooled crotonaldehyde is recorded by tuning the laser frequency around 355 nm. An oxetene type transient intermediate in the ground state has been considered for acetaldehyde formation following a photochemical model suggested earlier (Reguero ; et al. J. Am. Chem. Soc. 1994, 116, 2101-2114) for such compounds. Likewise, for methoxy radical formation, a trans-cis isomerization about the C═C double bond has been considered in a triplet surface. Electron ionization mass spectra of the compound are also recorded by varying the electron kinetic energy in the range 11-70 eV. Ionic fragments in the mass spectra of the two ionization processes are dramatically different. Our suggested mechanisms for isomerization and fragmentation channels are substantiated by density functional theory calculations. Combined experimental and calculated data lead us conclude that isomerization occurs in neutral potential energy surfaces prior to dissociation and photoionization.

Biocontrol of larval mosquitoes by Acilius sulcatus (Coleoptera: Dytiscidae).

BACKGROUND: Problems associated with resistant mosquitoes and the effects on non-target species by chemicals, evoke a reason to find alternative methods to control mosquitoes, like the use of natural predators. In this regard, aquatic coleopterans have been explored less compared to other insect predators. In the present study, an evaluation of the role of the larvae of Acilius sulcatus Linnaeus 1758 (Coleoptera: Dytiscidae) as predator of mosquito immatures was made in the laboratory. Its efficacy under field condition was also determined to emphasize its potential as bio-control agent of mosquitoes. METHODS: In the laboratory, the predation potential of the larvae of A. sulcatus was assessed using the larvae of Culex quinquefasciatus Say 1823 (Diptera: Culicidae) as prey at varying predator and prey densities and available space. Under field conditions, the effectiveness of the larvae of A. sulcatus was evaluated through augmentative release in ten cemented tanks hosting immatures of different mosquito species at varying density. The dip density changes in the mosquito immatures were used as indicator for the effectiveness of A. sulcatus larvae. RESULTS: A single larva of A. sulcatus consumed on an average 34 IV instar larvae of Cx. quinquefasciatus in a 24 h period. It was observed that feeding rate of A. sulcatus did not differ between the light-on (6 a.m. - 6 p.m.), and dark (6 p.m. - 6 a.m.) phases, but decreased with the volume of water i.e., space availability. The prey consumption of the larvae of A. sulcatus differed significantly (P < 0.05) with different prey, predator and volume combinations, revealed through univariate ANOVA. The field study revealed a significant decrease (p < 0.05) in larval density of different species of mosquitoes after 30 days from the introduction of A. sulcatus larvae, while with the withdrawal, a significant increase (p < 0.05) in larval density was noted indicating the efficacy of A. sulcatus in regulating mosquito immatures. In the control tanks, mean larval density did not differ (p > 0.05) throughout the study period. CONCLUSION: the larvae of the dytiscid beetle A. sulcatus proved to be an efficient predator of mosquito immatures and may be useful in biocontrol of medically important mosquitoes.

Primary extramedullary hematopoiesis manifesting as massive bilateral chylothorax.

Intrathoracic extramedullary hematopoiesis is a rare entity, mostly observed in patients with hematologic disorders. Extramedullary hematopoiesis is usually asymptomatic and is often located in the lower paravertebral sulci and rarely in the pleura. We report the case of a 54-year-old man without hematologic disorder or pleural malignancy who had a massive bilateral chylothorax develop due to primary pleural extramedullary hematopoiesis. He was successfully treated by bilateral video thoracoscopic talc pleurodesis and low-dose radiotherapy.

Nanoalloys based on clays: intercalated semicrystalline blends of syndiotactic polystyrene with poly(2,6-dimethyl-p-phenylene oxide).

Nanoalloys of syndiotactic polystyrene with poly(2,6-dimethyl-p-phenylene oxide) clay were prepared by a solution intercalation technique using 1,1,2,2-tetrachloroethane. A mixed intercalated/exfoliated morphology in the nanoalloys containing organo-clays is evinced by transmission electron microscopy. Thermal stability is found to improve with 5% by weight of organo-clays, but a reverse trend is observed by increasing the concentration of clay. The influence of montmorillonite clays in isothermal melt-crystallization behavior of blends was thoroughly investigated by using differential scanning calorimetry and wide-angle X-ray diffraction. A considerable change in polymorphic behavior of syndiotactic polystyrene is observed by the incorporation of different clays into the blends, and the temperature window of isothermal crystallization for the formation of a-crystals of syndiotactic polystyrene is found to broaden in the presence of organo-clays. In contrast, the pristine clay is found to induce only the beta-crystal of syndiotactic polystyrene at all the crystallization temperatures studied in this work. The amorphous component poly(2,6-dimethyl-p-phenylene oxide) affects the crystallinity of syndiotactic polystyrene adversely and favors the beta-form of syndiotactic polystyrene in blends; a-crystals are observed in the nano-alloys containing 20 wt% of poly(2,6-dimethyl-p-phenylene oxide). The crystalline morphology, as characterized by polarized optical microscopy, clearly indicates rapid formation of the alpha-form induced by the nanoscale dispersion of organo-clays in spherulites of smaller dimension.

Multidisciplinary management of giant malignant endo-thoracic nerve sheath tumor.

Malignant degeneration of neurogenic tumors has been reported to occur in 1-25% of patients with neurofibromatosis-I, and is the leading cause of cancer-related death in these patients. We report a case of multidisciplinary management of a giant malignant endothoracic nerve sheath tumor leading to histologically proven remission.

Predictors of stroke in the modern era of coronary artery bypass grafting: a case control study.

BACKGROUND: Stroke is a rare but devastating complication after coronary artery bypass grafting (CABG) and its prevention remains elusive. We used a case control design to investigate the extent to which preoperative and perioperative factors were associated with occurrence of stroke in a cohort of consecutive patients undergoing myocardial revascularization. METHODS: From April 1996 to March 2001, data from 4,077 patients undergoing CABG were prospectively entered into a database. The association of preoperative and perioperative factors with stroke was investigated by univariate analyses. Factors observed to be significantly associated with stroke in these analyses were further investigated using multiple logistic regression to estimate the strength of the associations with the occurrence of stroke, after taking account of the other factors. RESULTS: During the study period, 4,077 patients underwent CABG and of these 923 (22.6%) had off-pump surgery. Forty-five patients suffered a perioperative stroke (1.1%). Overall there were 46 in-hospital deaths (1.1%), of whom 6 also suffered a stroke. Brain imaging of the stroke patients showed embolic lesions in 58%, watershed in 28%, and mixed in 14%. Multivariate regression analysis identified several preoperative factors as independent predictors of stroke, ie, age, unstable angina, serum creatinine greater than 150 mcg/ml, previous cerebrovascular accident (CVA), peripheral vascular disease (PVD), and salvage operation. When operative risk factors were added to the adjusted model, off-pump surgery was associated with a substantial, but not significant, protective effect against stroke (odds ratio = 0.56, 95% confidence interval 0.20 to 1.55). Survival for stroke patients was 93% and 78% at 1 and 5 years, respectively. CONCLUSIONS: Overall incidence of stroke is relatively low in our series. Age, unstable angina, previous CVA, PVD, serum creatinine greater than 150 mcg/ml, and salvage operation are independent predictors of stroke. These factors should be taken into account when informing each individual patient on the possible risk of stroke and in the decision-making process on the surgical strategy.